Match



Patented June 11, 1935 I UNITED STATES PATENT OFFICE MATCH Alphons 0. Jaeger, Mount Lebanon, Pa., assignor, by mesne assignments, to American Cyanamid & Chemical Corporation, a corporation of Delaware x No Drawing. Application December 9, 1931, 1 Serial No. 579,987

4 Claims. (CL 52425) This invention relates to improvements in pyro- Serial No. 551,798 filed July 18, 1931 and Serial technic and match compositions and more spe- No. 552,075 filed July 20, 193l,which are well cifically to methods of protecting such products suited for use in the present inventionagainst deterioration from moisture. Similarly, an excellent class of coating mate- 5 According to the invention compositions su h rials can be obtained by-combina ion f the as matches, both safety matches and those of the rious classes of resins, ith r modified 11nm0di-' strike anywhere varietyas well as pyrotechnic fied. As a result of such mixtures the various compositions such as fireworks and explosives outstanding physical properties of the different are protected from moisture by spraying, dipping resins are combined, for example the stability,

or otherwise coating them with compositions consoftness and non-inflannnability of the polyhy- 1 taining synthetic resinous materials. It has been dric alcoho Dolybasic acids'serve to modify the proposed to use parafiins and waxes for similar brittle, hard, h y inflammable nitrocellulose purposes but these are open to many objections resins to produce a coating material which will since they tend to soften in'the presence of heat burn in the presence f a match flame but will 1:; and require quite a. bulky coating to effect the not tend to ignite spontaneously and which will 15 desired purpose. Synthetic resinous materials, produce a sufficiently hard and flexible coating on the other hand, whether taken up in solvents to protect the match during shipping and use. to form lacquers or used as such, can be much Similarly, the hard, dense and non-inflammable more effective in lesser amounts and the wide phenolaldehyde resins may be combined with the range of choice permits obtaininga material exnitrocellulose resins, with or without the addi- 20 actly suited for each individual purpose. tion of glyptal resins.

It has also been proposed to use nitrocellulose A further modification of the coating by incoras a coating composition but the nitrocellulose is poration of plasticizers or softeners. is also of not desirable in most cases as it is too violently value. Almost any of the usual softening agents combustible and requires excessive cost in solfor resinous compositions may be used for this 25 vents owing to the extraordinary viscosity of purpose, high boil ng es e phthalic esters nitrocellulose solutions as compared to solutions such as diethyl phthalate, phthalides, esters and of Sy thetic resins. salts of keto aromatic acid, tricresyl phosphate The invention is not limited to any definite and the like being particularly useful. Additional class of synthetic resinous'materials, but on the softness may be obtained by physically inCOT- 30 contrary any desired synthetic resin or mixture porating oils, fats or waxes such as beeswax,

of such resins ay e p oyed to produce suitparaflin, stearine, etc., into the resin, which may able protective coatings. Such substances are also contain other softeners and may be modified polyhydric alcohol-polybasic acid resins, phenolor unmodified.

aldehyde, phenol-furfural and urea resins, nitro- Resinous materials such as .those described 35 cellulose resins, coumarone resins, indene resins, constitute adecided improvement over other provinyl resins, styrol resins, or mixtures of these are tective coatings, for their stability, hardness and especially useful and present the added advan high resistance to moisture permits a much tages of low initial cost and solubility in cheap thinner-coating to be used. So thin is this coat- 40 solvents. While in many cases unmodified resins ing that upon striking the match or upon ignition 4 such as the above may be suitable, a closer adof other pyrotechnic compositions the thin pro.- justment of the desired properties to the requiretective coating is quickly worn or burned through, ments of the particular pyrotechnic 'or match to and consequently the striking quality of matches be coated may be obtained by the use of modiand the readyignition of other pyrotechnics is l fied resins. For example, the polyhydric alcoholnot impaired. l polybasic acid resins may be modified by the in: In addition to their protective action, the coatcorporation during their preparation of aliphatic ing compositions used in the present invention dibasic acids such as succinic, maleic or adipic are excellently suited for the incorporation of acids or monobasic acids such as benzoic, abietic, dyes, thus greatly improving the appearance of lactic, salicylic, fat acids, etc., as well as balsam I the product. Almost any-desired type of dye may ro D aand other components of be used, those'resulting from the condensation of the modified glyptal resins sold on the market as quinones such as alphanaphthoquinone with Rezyls. O r m d fyi agents may also be amines such as aniline being excellently suited used, such as, for example, the phthalides such by reason of their ready solubility. Soluble color as those described in my copending applications lakes, such as those resulting from the reaction game of solutions of metallo-organic compounds in orsolvents with solutions of lake forming poses only and to which it is not limited.

Example 1- A modified glyptal resin is prepared by heating a mixture of 202 parts phthalic anhydride, 40.5 parts phthalide and 92 parts glycerin for 23 hours at C. or until the desired degree of esteriflcation has been reached. The product, in molten state or dissolved in alcohol, is coated onto ordinary kitchen or strike anywhere matches, by dipping the match heads into the liquid. Of course the entire match may be so coated, but usually a coating over the match head is sufficient. After hardening of the resin the matches may be immersed in water for one-half hour or longer and will still light when scratched against a rough surface. 1

The proportion of phthalide to phthalic anhydride may be varied in order to vary the hardness of the resinous coating. Thus, for example, a slightly softer resin is produced by using 60.5 parts of phthalide and 191 parts phthalic anhydride in the above preparation, and still greater plasticity is obtained by using 82 parts phthalide,

180 parts phthalic anhydride to 92 parts glycerin. Plasticizerssuch as diethyl phthalate may also 'be addedto the solution if desired.

Corresponding amounts of other modifying agents may also be used, such as succinic acid,

, benzoic acid, cottonseed oil, and other fat acids,

etc. By this means, resinous coatings of any desired degree of hardness may be obtained. A dye, such as 2-anilidonaphthoquinone may be added in small amounts to give a red color to th coating if desired.

- Examplez A mixture of 90 parts by weight of glycerin, 195 parts phthalic anhydride and 18-24 parts rosin are heated to I'm-185 C. until reaction ceases and a clear product is obtained. The resin so obtained is dissolved in acetone, amyl acetate or an alcohol and 50-75 parts nitrocellulose, cellulose acetate or cellulose ether, are stirred in. The solution is thinned to the proper consistency, preferably using benzol, toluol or other cheap solvent, and is applied to safety matches, either of the cardboard variety or those having a wooden stick. The coating, after drying in air, is hard and brilliant and protects the match against moisture. Similarly, a thin coating may be applied to the striking surface on the match con- .tainer to prevent softening and deterioration by moisture.

The coating composition may be made more flexible by the addition of suitable plasticizers such as high boiling esters, e. g., diethyl or dibutyl phthalate; or phthalide, substituted phthalides or hydrogenated phthalides may be used. Esters of keto aromatic acids, such as the methyl, ethyl or propyl esters of benzoyl benzoic or naphthoyl benzoic acid may also be used as plasticizers.

Similar coating compositions may be applied to other pyrotechnics such as roman candles, skyrockets, pinwheels, stick dynamite, flares, torpedoes, percussion caps, fuses, etc., by treating with suitable solutions, drying and hardening.

Example 3 match.

If desired, cellulose plastics such as cellulose acetate, cellulose ethers, etc. may be dissolved in the solvent in amounts up to 40-50% of the phenol-formaldehyde resin. Similarly, artificial plastics, plastics of other types such as vinyl resins, urea resins, etc. may be used if desired.

What is claimed as new is:

1. A match, the head of which is provided with a coating comprising as a major constituent a synthetic resin selected from the group consisting of ,polyhydric alcohol-polybasic acid resins and phenol-aldehyde resins, said coating being substantially impervious to moisture but being so thin as to have no eifect on the striking qualities of the match.

2. A match, the head of which is provided with a coating comprising as a major constituent a plasticized synthetic resin selected from the group consisting of polyhydric alcohol-polybasic acid resins and phenol-aldehyde. resins, said coating being substantially impervious to moisture but being so thin as to have no effect on the striking qualities of the match.

3. A match, the head of which is provided with plasticized glycerol-phthalic anhydride resin, said coating being substantially impervious to moisture but being so thin as to have no effect on the striking qualities of the match.

4. A match, the head of which is provided with I a coating comprising as a major constituent a r 

